新能源汽车电池用无镁储氢合金的制备与性能研究

doi:10.19964/j.issn.1006-4990.2021-0052

摘要/Abstract

摘要：

采用真空电弧熔炼和925 ℃/12 h退火的方法制备了Y_1-_xLa_xNi_3.25Al_0.15Mn_0.15储氢合金（x=0~1）,研究了x值对储氢合金物相组成和电化学性能的影响。结果表明,x=0和0.15的储氢合金主要由LaNi₅和Ce₂Ni₇相组成,x=0.25、0.33和0.5储氢合金主要由Ce₅Co₁₉和Ce₂Ni₇相组成,x=0.75和1储氢合金主要由PuNi₃、LaNi₅和Ce₂Ni₇相组成;相同充放电循环周次下,x=0.15~1储氢合金的放电容量和抗氢致非晶化能力都高于x=0储氢合金,且随着x从0增加至1,储氢合金的最大放电容量（C_max）、容量保持率（S₁₀₀）、氢扩散系数（D₀）和高倍率放电性（HRD₉₀₀）都呈现先增加后减小趋势,在x=0.33时取得C_max、S₁₀₀、D₀和HRD₉₀₀最大值。Y_1-_xLa_xNi_3.25Al_0.15Mn_0.15储氢合金的循环稳定性与合金电极的耐腐蚀性密切相关,高倍率放电性能取决于储氢合金的氢扩散速率。

关键词: 储氢合金, 新能源汽车, 电池, 电化学性能

Abstract:

Y_1-_xLa_xNi_3.25Al_0.15Mn_0.15 hydrogen storage alloy（x=0~1） was prepared by vacuum arc melting and annealing at 925 ℃ for 12 h.The effect of x value on the phase composition and electrochemical properties of hydrogen storage alloy was studied.The results showed that hydrogen storage alloys with x=0 and 0.15 were mainly composed of LaNi₅ and Ce₂Ni₇ phases;hydrogen storage alloys with x=0.25,0.33 and 0.5 were mainly composed of Ce₅Co₁₉ and Ce₂Ni₇ phases;hydrogen storage alloys with x=0.75 and 1 were mainly composed of PuNi₃,LaNi₅ and Ce₂Ni₇ phases;under the same charge discharge cycle,the discharge capacity and anti hydrogen induced amorphization ability of hydrogen storage alloy with x=0.15~1 were higher than that of hydrogen storage alloy with x=0,and with the increase of x value from 0 to 1,C_max,S₁₀₀,D₀ and HRD₉₀₀ of hydrogen storage alloy increased at first and then decreased,and the maximum values of C_max,S₁₀₀,D₀ and HRD₉₀₀ were obtained at x=0.33.The cycle stability of Y_1-_xLa_xNi_3.25Al_0.15Mn_0.15 hydrogen storage alloy was closely related to the corrosion resistance of the alloy electrode, and the high rate discharge performance depended on the hydrogen diffusion rate of the hydrogen storage alloy.

Key words: hydrogen storage alloy, new energy vehicle, battery, electrochemical performance

中图分类号:

TQ138.13

程丽群,左付山. 新能源汽车电池用无镁储氢合金的制备与性能研究[J]. 无机盐工业, 2021, 53(11): 71-76.

CHENG Liqun,ZUO Fushan. Study on preparation and properties of magnesium free hydrogen storage alloys for new energy vehicle batteries[J]. Inorganic Chemicals Industry, 2021, 53(11): 71-76.

图/表 12

图1

表1

图2

图3

图4

图5

图6

图7

表2

图8

图9

图10

参考文献 23

[1]	OUYANG L Z, HUANG J L, WANG H, et al. Progress of hydrogen storage alloys for Ni-MH rechargeable power batteries in electric vehicles:A review[J]. Materials Chemistry & Physics, 2017, 200:164-178.
[2]	徐津, 闫慧忠, 王利, 等. La-Y-Ni系储氢合金材料的研究进展[J]. 稀土, 2020, 41(5):114-122.
[3]	DAVID P, LUIS V, JAVIER P, et al. A review on the role,cost and value of hydrogen energy systems for deep decarbonisation[J]. Rene-wable & Sustainable Energy Reviews, 2019, 101:279-294.
[4]	徐津, 李宝犬, 王利, 等. A2B7型La-Y-Ni与La-Mg-Ni储氢合金电化学性能研究[J]. 有色金属工程, 2020, 10(12):9-15.
[5]	DYMEK M, NOWAK M, JURCZYK M, et al. Encapsulation of La_1.5Mg_0.5Ni₇ nanocrystalline hydrogen storage alloy with Ni coatings and its electrochemical characterization[J]. Journal of Alloys and Compounds, 2018, 749:534-542. doi: 10.1016/j.jallcom.2018.03.230
[6]	孙艳, 罗永春. 钇对AB5型La_(0.7-_x)Y_xCe_0.3Ni_3.9Co_0.45Mn_0.35Al_0.3储氢合金的组织和电化学性能的影响[J]. 中国稀土学报, 2020, 38(5):640-645.
[7]	熊玮, 张旭, 周淑娟, 等. 不同物质的量比La-Y-Ni系储氢合金的研究Ⅰ:表面状态与组织结构[J]. 稀土, 2020, 41(6):9-17.
[8]	赵红霞, 张羊换, 冯佃臣. La₍₂-_x)Pr_xMg₁₆Ni+100%Ni(x=0.1~0.4)储氢合金电化学性能和动力学性能研究[J]. 内蒙古科技大学学报, 2019, 38(1):22-28.
[9]	陶炳全, 张华, 杨星焕, 等. 汽车氢镍电池负极材料的热处理与性能研究[J]. 电源技术, 2020, 44(11):1642-1646.
[10]	郭淼, 苑慧萍, 刘彧儒, 等. 热处理温度对La-Y-Ni合金相结构和电化学性能的影响[J]. 无机化学学报, 2019, 35(6):1041-1049.
[11]	马玉蕊, 董小平, 陈亚方, 等. La-Mg-Ni系储氢合金的容量衰减与组织结构[J]. 科学技术与工程, 2020, 20(25):10214-10218.
[12]	董振伟, 熊海岩, 石仪超, 等. 复相La-Mg-Ti-Ni-Co基AB3型储氢合金的相结构与电化学性能衰退机理研究[J]. 化工新型材料, 2019, 47(7):174-177.
[13]	史云斌, 黄瑞. 混合动力汽车用镁基储氢合金制备与性能研究[J]. 铸造技术, 2018, 39(2):302-305.
[14]	宋飞, 罗丹. 混合动力车电池用镁基储氢合金的制备及性能[J]. 金属热处理, 2017, 42(12):90-94.
[15]	王浩, 罗永春, 邓安强, 等. La-Mg-Ni系A2B7型储氢合金表面包覆NAFION及其电化学性能研究[J]. 金属功能材料, 2018, 25(1):23-29.
[16]	董振伟, 张帅阳, 马榕彬, 等. La₍₁-_x)Mg_xNi_2.5Co_0.5(x=0~0.4)储氢合金的制备及电化学氢化性能[J]. 材料科学与工程学报, 2018, 36(4):573-577.
[17]	王浩, 罗永春, 邓安强, 等. 退火温度对无镁La-Y-Ni系A2B7型合金相结构和电化学性能的影响[J]. 无机材料学报, 2018, 33(4):434-440. doi: 10.15541/jim20170222
[18]	邢磊, 李一鸣, 张羊换, 等. 快淬-退火La₄MgNi₁₉合金的电化学储氢性能及其失效行为[J]. 稀有金属, 2017, 41(12):1318-1326.
[19]	郭淼, 苑慧萍, 沈浩, 等. Mn,Al元素替代对A2B7型La-Y-Ni储氢合金的影响[J]. 稀有金属, 2019, 43(8):824-830.
[20]	卿培林, 韦宁燕, 蓝志强, 等. 镨部分替代镧对Mm-Mg-Ni合金电化学性能影响的研究[J]. 中国稀土学报, 2019, 37(3):344-350.
[21]	LIU J P, LI Y, HAN D, et al. Electrochemical performance and ca-pacity degradation mechanism of single-phase La-Mg-Ni-based hydrogen storage alloys[J]. Journal of Power Sources, 2015, 300:77-86. doi: 10.1016/j.jpowsour.2015.09.058
[22]	GAO Z J, BO Z, LUO Y C, et al. Correlation between phase struc-ture and electrochemical properties of Ce₂Ni₇-type La-RE-Mg-Ni(RE=Nd,Sm,Y) alloys:A comparative study[J]. Journal of the Taiwan Institute of Chemical Engineers, 2018, 89:183-190. doi: 10.1016/j.jtice.2018.05.013
[23]	LI W, ZHANG B, YUAN J, et al. Effect of Mo content on the micro-structures and electrochemical performances of La_0.75Mg_0.25Ni_3.2-_xCo_0.2Al_0.1Mo_x(x=0,0.10,0.15,0.20) hydrogen stor-age alloys[J]. Journal of Alloys & Compounds, 2017, 692:817-824.

x	相类型	点阵常数		相质量分数/%
x	相类型	a/nm	c/nm	相质量分数/%
0	LaNi₅	0.502 3	0.398 3	47.25
0	Ce₂Ni₇	0.499 3	2.441 6	52.75
0.15	LaNi₅	0.501 5	0.400 6	38.62
0.15	Ce₂Ni₇	0.500 3	2.432 5	61.38
0.25	Ce₅Co₁₉	0.494 5	4.878 5	20.98
0.25	Ce₂Ni₇	0.502 2	2.439 7	79.02
0.33	Ce₂Ni₇	0.502 6	2.435 8	93.07
0.33	Ce₅Co₁₉	0.498 7	4.861 2	6.93
0.5	Ce₅Co₁₉	0.491 4	4.868 0	37.76
0.5	Ce₂Ni₇	0.502 1	2.432 9	62.24
0.75	PuNi₃	0.502 7	2.432 1	27.87
	LaNi₅	0.502 7	0.406 5	11.38
	Ce₂Ni₇	0.499 2	2.458 0	60.75
1	PuNi₃	0.499 9	2.436 5	17.37
	LaNi₅	0.506 9	0.402 5	33.42
	Ce₂Ni₇	0.499 8	2.458 9	49.11

x	活化次数	C_max/ （mA·h·g^-1）	容量保持率 S₁₀₀/%	高倍率放电性能 HRD₉₀₀/%	氢扩散系数D₀ / （10^-10 cm²·s^-1）	电流密度/ （mA·cm^-2）	腐蚀电位/ V
0.00	4	172.7	14.34	68.23	1.05	8.758	-0.946
0.15	4	345.7	33.70	75.11	1.82	8.749	-0.938
0.25	4	364.2	74.02	82.77	2.67	6.585	-0.923
0.33	3	372.6	89.01	83.53	2.80	5.821	-0.922
0.50	3	337.4	77.98	75.73	1.43	6.801	-0.926
0.75	2	191.4	78.36	74.55	1.12	6.702	-0.930
1.00	2	197.4	79.06	81.03	1.39	6.747	-0.927

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会